Molybdenum Containing Catalyst Utilized Patents (Class 568/479)
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Patent number: 4620035Abstract: Production of acrylic acid by oxidation of acrolein with gas containing oxygen in the gas phase at elevated temperature in the presence of a catalyst which, in addition to oxygen, consists essentially of (a) molybdenum, (b) tungsten, (c) vanadium and (d) iron and/or copper. The atomic ratio of molybdenum:tungsten:iron and/or copper is 1 to 20:0.01 to 10:1 and the atomic ratio of vanadium:molybdenum is 0.2 to 6:6. Acrylic acid is an important starting material for the production of high polymers.Type: GrantFiled: October 9, 1981Date of Patent: October 28, 1986Assignee: BASF AktiengesellschaftInventors: Richard Krabetz, Heinz Engelbach
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Patent number: 4618593Abstract: A regeneration process for tellurium-containing metal oxide catalysts used in the process for oxidation, ammoxidation or oxidative dehydrogenation of organic compounds at a temperature of about 300.degree. C. to about 600.degree. C. The process can be effectively applied to such catalysts which have become partially deactivated during the reaction.Type: GrantFiled: May 17, 1982Date of Patent: October 21, 1986Assignee: Nitto Chemical Industry Co., Ltd.Inventors: Yutaka Sasaki, Yutaka Kiyomiya, Toshio Nakamura
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Patent number: 4604370Abstract: A process for regenerating a Mo.Bi-based multi-oxide catalyst the catalytic performance of which has deteriorated as a result of its use in vapor-phase catalytic oxidation of propylene or isobutene to prepare acrolein or methacrolein, respectively, which process comprises: heating the deteriorated Mo.Bi-based multi-oxide catalyst in an atmosphere consisting essentially of air at a temperature of 380.degree. C. to 540.degree. C., so as to attain at least partial restoration of the catalytic performance thereof.Type: GrantFiled: July 9, 1985Date of Patent: August 5, 1986Assignee: Mitsubishi Petrochemical Company, LimitedInventors: Kohei Sarumaru, Takeshi Shibano, Yoichi Ishii, Etsuji Yamamoto
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Patent number: 4564703Abstract: In a process for preparing methacrylic acid by the vapor-phase catalytic oxidation of methacrolein or a methacrolein-containing mixture with molecular oxygen in the presence of an oxidation catalyst; the improvement wherein said process comprisesa first-stage oxidation step of oxidizing methacrolein or a methacrolein-containing mixture as a starting material,a first-stage separating step of separating the resulting methacrylic acid from the reaction product obtained in the first-stage oxidation step,a second-stage oxidation step of oxidizing the mixture containing the unreacted methacrolein and obtained in the first-stage separating step, anda second-stage separating step of separating the resulting methacrylic acid from the reaction product obtained in the second-stage oxidation step, andwith or without at least one additional oxidation step and separating step subsequent to the second-stage separating step,and wherein the conversion of methacrolein in the first-stage oxidation step is adjusted to 30-85 moleType: GrantFiled: April 16, 1979Date of Patent: January 14, 1986Assignee: Nippon Zeon Co., Ltd.Inventors: Haruhisa Yamamoto, Shinichi Akiyama
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Patent number: 4556731Abstract: Iron-bismuth-molybdate catalysts further containing specific promoter elements have been found to exhibit excellent redox stability even under high stress conditions in the catalytic oxidation of olefins to unsaturated aldehydes and acids.Type: GrantFiled: April 19, 1982Date of Patent: December 3, 1985Assignee: The Standard Oil CompanyInventors: Andrew T. Guttmann, Robert K. Grasselli
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Patent number: 4537874Abstract: A catalyst for the production of unsaturated aldehydes is provided which is represented by the general formulaBi.sub.a W.sub.b Fe.sub.c Mo.sub.d A.sub.e B.sub.f C.sub.g D.sub.h O.sub.xwherein Bi represents bismuth, W represents tungsten, Fe represents iron, Mo represents molybdenum, O represents oxygen, A represents nickel and/or cobalt, B represents at least one element selected from the group consisting of alkali metals, alkaline earth metals and thallium, C represents at least one element selected from the group consisting of phosphorus, arsenic, boron, antimony, tin, cerium, lead and niobium, D presents at least one element selected from the group consisting of silicon, aluminum, zirconium and titanium, a, b, c, d, e, f, g, h and x represent the atomic ratios of the individual elements, and when d is taken as 12, a=0.1-10.0, b=0.5-10.0 (provided that a/b=0.01-6.0), c=0.1-10.0, e=2.0-20.0, f=0.001-10.0, g=0-10.0, and h=0-30, and x takes a number determined by the atomic valences of the individual elements.Type: GrantFiled: October 18, 1983Date of Patent: August 27, 1985Assignee: Nippon Shokubai Kagaku Kogyo Co LtdInventors: Takahisa Sato, Masahiro Takata, Michio Ueshima, Isao Nagai
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Patent number: 4535188Abstract: Isobutane in a C.sub.4 hydrocarbon feed stream is converted to methacrolein in an integrated two-step process. Isobutane is dehydrogenated in a first step to isobutylene, hydrogen, and by-products and the reaction effluent is passed directly into a second step where isobutylene is oxidized to methacrolein without significant oxidation of the hydrogen and by-products. Any normal butenes present are converted to butadiene. The methacrolein and by-products may be separated and the unreacted isobutylene and isobutane recycled to the first step. Alternatively, the effluent from the second step may be used as feed to a further oxidation step for conversion of methacrolein to methacrylic acid.Type: GrantFiled: September 20, 1982Date of Patent: August 13, 1985Assignee: The Halcon SD Group, Inc.Inventor: Sargis Khoobiar
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Patent number: 4532365Abstract: Alkanes, particularly propane and isobutane are converted to unsaturated aldehydes, particularly acrolein and methacrolein in an integrated two-step process wherein the alkane is dehydrogenated in a first step to the corresponding olefin, hydrogen, and by-products and the reaction effluent is passed directly into a second step where the olefin is oxidized to the corresponding unsaturated aldehyde without significant oxidation of the hydrogen and by-products. The aldehydes and by-products may be separated and the unreacted olefin and alkane recycled to the first step. Alternatively, the effluent from the second step may be used as feed to a further oxidation step for conversion of the unsaturated aldehyde to the corresponding unsaturated acid.Type: GrantFiled: February 22, 1983Date of Patent: July 30, 1985Assignee: The Halcon SD Group, Inc.Inventor: Sargis Khoobiar
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Patent number: 4528398Abstract: The present invention relates to a method for the preparation of phosphomolybdic acid based catalysts utilized in the oxidation of aldehydes to unsaturated carboxylic acids by forming a solution of hydrated phosphomolybdic acid in a substantially anhydrous alkanol, adding a base to the solution, evaporating the solution to yield a catalyst powder and thereafter drying and calcining the powder to form the active catalyst. A second method for preparation is also provided and includes the steps of forming a solution of hydrated phosphomolybdic acid in a substantially anhydrous alkanol, evaporating the solution to form a concentrate, impregnating a catalyst support material with the concentrate, contacting the impregnated support with ammonia gas in an amount sufficient to form an insoluble precipitate of ammonium alkyl phosphomolybdic acid within the pore structure of said support material and thereafter drying and calcining said impregnated support material so as to form a coated catalyst.Type: GrantFiled: November 18, 1982Date of Patent: July 9, 1985Assignee: The Standard Oil Company (Ohio)Inventors: James L. Callahan, Wilfrid G. Shaw, Arthur F. Miller
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Patent number: 4526992Abstract: The synthesis of substituted dioxolanes by direct oxidation of olefins over a molybdenum 8-hydroxyquinoline catalyst in the presence of water is described. An organic solvent such as chlorobenzene may also be employed. Water is essential to the reaction to make the dioxolanes, otherwise olefin oxides are produced. Hence, 4-methyl-1,3-dioxolane and 2,4-dimethyl-1,3-dioxolane were prepared from propylene oxidation, and three isomers of 2,4,5-trimethyl-1,3-dioxolane were prepared from 2-butene oxidation.Type: GrantFiled: October 18, 1984Date of Patent: July 2, 1985Assignee: Texaco, Inc.Inventors: Jiang-Jen Lin, John R. Sanderson
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Patent number: 4511671Abstract: A catalyst for manufacturing methacrolein by the vapor phase oxidation of isobutylene or tertiary butanol, said catalyst having the composition represented by the following formulaMo.sub.a W.sub.b Bi.sub.c Fe.sub.d A.sub.e B.sub.f C.sub.g D.sub.h O.sub.xwhereinA represents at least one element selected from the group consisting of nickel and cobalt,B represents at least one element selected from the group consisting of alkali metals, alkaline earth metals and thallium,C represents at least one element selected from the group consisting of tellurium, antimony, tin, cerium, lead, manganese and zinc,D represents at least one element selected from the group consisting of silicon, aluminum, zirconium and titanium,a, b, c, d, e, f, g, h, and x respectively represent the atomic ratios of Mo, W, Bi, Fe, A, B, C, D, and O, and whena is fixed at 12,b is from 0 to 10,c is from 0.1 to 10,d is from 0.Type: GrantFiled: September 1, 1983Date of Patent: April 16, 1985Assignee: Nippon Shokubai Kagaku Kogyo Co., Ltd.Inventors: Noboru Saito, Takeshi Satake, Ryuji Aoki, Isao Nagai
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Patent number: 4499301Abstract: Vapor phase process for the preparation of unsaturated aldehydes, carboxylic acids and mixtures thereof which comprises contacting a gaseous mixture of an open-chain olefin of from 3 to 8 carbon atoms, water and oxygen at an elevated temperature up to about 250.degree. with a solid catalyst comprising a catalytically effective amount of noble metal promoted by a solid acid consisting of mixed metal oxides.Type: GrantFiled: May 14, 1982Date of Patent: February 12, 1985Assignee: National Distillers and Chemical CorporationInventor: Jawad H. Murib
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Patent number: 4487850Abstract: Catalysts useful for the oxidation and ammoxidation of olefins contain antimony, uranium, iron, bismuth, and molybdenum in a catalytically active oxidized state. The catalysts are especially useful for the production of acrylonitrile from propylene, ammonia, and an oxygen-containing gas.Type: GrantFiled: April 9, 1984Date of Patent: December 11, 1984Assignee: Monsanto CompanyInventor: Tao P. Li
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Patent number: 4479014Abstract: Isobutane in a C.sub.4 hydrocarbon feed stream is converted to methacrolein in an integrated two-step process. Isobutane is dehydrogenated in a first step to isobutylene, hydrogen, and by-products and the reaction effluent is passed directly into a second step where isobutylene is oxidized to methacrolein without significant oxidation of the hydrogen and by-products. Any normal butenes present are converted to butadiene. The methacrolein and by-products may be separated and the unreacted isobutylene and isobutane recycled to the first step. Alternatively, the effluent from the second step may be used as feed to a further oxidation step for conversion of methacrolein to methacrylic acid.Type: GrantFiled: September 20, 1982Date of Patent: October 23, 1984Assignee: The Halcon SD Group, Inc.Inventor: Sargis Khoobiar
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Patent number: 4479013Abstract: A catalyst composition useful for the oxidation of olefins, particularly the vapor phase oxidation of isobutylene and/or tertiary butyl alcohol to produce methacrolein, consists essentially of the combination of oxides of molybdenum, cobalt, iron, bismuth, thallium, antimony, silicon, and nickel, along with one or more members of the groups consisting of the alkali metals, the alkaline earth metals, the rare earth metals including lanthanum, tungsten, and mixtures thereof. The catalyst has a BET surface area within the range of about 0.5-10 m.sup.2 /gm and preferably within the range of about 2-6 m.sup.2 /gm. Preferably, the catalyst has no more than about 3% of the surface area associated with pores smaller than about 100 .ANG.. The catalyst is heated during its preparation to a temperature above 525.degree. C., preferably above 550.degree. C., most preferably to about 600.degree. C.Type: GrantFiled: July 9, 1982Date of Patent: October 23, 1984Assignee: The Halcon SD Group, Inc.Inventor: Sargis Khoobiar
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Patent number: 4473506Abstract: Oxide complex catalysts of iron, selenium and tellurium provide good yields of acrylonitrile in the ammoxidation of propylene with high selectivities at low temperature.Type: GrantFiled: October 18, 1982Date of Patent: September 25, 1984Assignee: The Standard Oil CompanyInventors: James D. Burrington, James F. Brazdil, Robert K. Grasselli
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Patent number: 4453006Abstract: A method for preparing attrition resistant, high percentage active component catalysts comprises using two types of silica, one of which is fumed silica, in a two stage catalyst preparation.Type: GrantFiled: February 12, 1981Date of Patent: June 5, 1984Assignee: The Standard Oil CompanyInventors: Wilfrid G. Shaw, Christos Paparizos, James L. Callahan
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Patent number: 4446328Abstract: A process for producing methacrolein by oxidizing isobutylene or tertiary butanol with molecular oxygen, characterized by contacting a gaseous mixture of isobutylene or tertiary butanol, air or oxygen and optionally steam and an inert gas with a catalyst having the general composition:Mo.sub.12 Fe.sub.a Ni.sub.b Te.sub.c X.sub.d Z.sub.f Y.sub.g O.sub.hwherein a, b, c, d, f and g represent the numbers of atoms of the respective elements per 12 molybdenum atoms; X is Tl, Rb or Cs; Z is In or Ti; Y represents at least one element selected from the group consisting of Cu, Nd, Sm and Pb; a is a value of 0.2-6; b is a value of 0.2-6; a+b is a value of 1-10; c is a value of 0.1-4; d is a value of 0.1-3; f is a value of 0.1-3; g is a value of 0-5; and h is the number of oxygen atoms for satisfying the valencies of the existing elements. The use of this catalyst enables the selectivity for methacrolein to be improved to 90 or more and the yield based on the starting material to be increased to 89-91%.Type: GrantFiled: May 14, 1981Date of Patent: May 1, 1984Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Atsushi Aoshima, Ryoichi Mitsui
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Patent number: 4442308Abstract: A process is disclosed for preparing acrolein from propylene and methacrolein from isobutylene or tertiary butanol, by oxidation in oxygen-containing gas mixtures on specially prepared coated catalysts comprised of an inert support and a coating, enclosing this support, of an oxidic catalyst material containing the elements nickel, cobalt, iron, bismuth, phosphorus, molybdenum and tantalum or samarium and, if appropriate, also alkali metal or alkaline earth metal in certain atomic ratios. This coated catalyst is obtained by spraying a suspension of the starting material for the coating, which suspension contains a binder and, if appropriate, a pore-former, from above in an increasing amount onto a bed of the support, which bed is mechanically agitated and loosened up by a gas stream blow in from below, the ratio between suspending medium sprayed on and removed again by the gas stream remaining approximately constant.Type: GrantFiled: June 21, 1982Date of Patent: April 10, 1984Assignee: Degussa AktiengesellschaftInventors: Dietrich Arntz, Gunter Prescher, Johannes Heilos
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Patent number: 4442307Abstract: A process is disclosed for oxidizing dimethyl ether to formaldehyde using a catalyst comprising a mixture of oxides of bismuth, molybdenum and iron.Type: GrantFiled: October 7, 1982Date of Patent: April 10, 1984Assignee: Shell Oil CompanyInventors: Robert M. Lewis, Robert C. Ryan, Lynn H. Slaugh
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Patent number: 4439624Abstract: A process is disclosed for oxidizing dimethyl ether to formaldehyde using a catlyst comprising a mixture of oxides of bismuth, molybdenum and copper.Type: GrantFiled: October 7, 1982Date of Patent: March 27, 1984Assignee: Shell Oil CompanyInventors: Robert M. Lewis, Robert C. Ryan, Lynn H. Slaugh
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Patent number: 4438217Abstract: A catalyst for the oxidation of propylene, said catalyst having the composition represented by the following formulaMo.sub.a W.sub.b Bi.sub.c Fe.sub.d A.sub.e B.sub.f C.sub.g D.sub.h O.sub.xwhereinA represents at least one element selected from the group consisting of nickel and cobalt,B represents at least one element selected from the group consisting of alkali metals, alkaline earth metals and thallium,C represents at least one element selected from the group consisting of phosphorus, arsenic, boron and niobium,D represents at least one element selected from the group consisting of silicon, aluminum and titanium,a, b, c, d, e, f, g, h, and x respectively represent the atomic ratios of Mo, W, Bi, Fe, A, B, C, D, and O,a is from 2 to 12,b is from 0 to 10,the sum of a and b is 12,c is from 0.1 to 10.0,d is from 0.1 to 10.0,e is from 2 to 20,f is from 0.005 to 3.0,g is from 0 to 4,h is from 0.Type: GrantFiled: December 30, 1982Date of Patent: March 20, 1984Assignee: Nippin Shokubai Kagako Kogyo Co., Ltd.Inventors: Masahiro Takata, Ryuji Aoki, Takahisa Sato
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Patent number: 4424141Abstract: Bismuth molybdate catalysts formed from a precatalyst slurry which uses an organic liquid or mixture of an organic liquid and water as the liquid medium of the slurry exhibit superior catalytic properties.Type: GrantFiled: January 5, 1981Date of Patent: January 3, 1984Assignee: The Standard Oil Co.Inventors: Robert K. Grasselli, Dev D. Suresh, Maria S. Friedrich
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Patent number: 4404397Abstract: A stabilized heteropoly molybdate catalyst precursor in calcined form and containing anionic molybdenum in defect state is surface impregnated with certain metal cations. The stabilized precursor is one obtained by incorporating into the reaction product of a molybdate and a soluble phosphate, silicate or arsenate, an aqueous chloride ion and a compound of phosphotungstate, silicotungstate, vanadium arsenate, silico-arsenate, phosphovanadate, or silicovanadate, followed by drying and calcining. During the chloride ion stabilization step other metals may be optionally incorporated in forming the stabilized precursor.The obtained precursor is catalytically active in the conversion of the unsaturated aldehydes to the corresponding unsaturated carboxylic acids with or without incorporation of the metal cation during the chloride ion stabilization step.Type: GrantFiled: December 29, 1980Date of Patent: September 13, 1983Assignee: Air Products and Chemicals, Inc.Inventor: Chelliah Daniel
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Patent number: 4365087Abstract: In the production of acrylic acid by a two-stage, vapor-phase catalytic oxidation of propylene, a composite oxide catalyst expressed by the formula Mo.sub.a Bi.sub.b Ni.sub.c Co.sub.d Fe.sub.e Na.sub.f Mn.sub.g B.sub.h K.sub.i Si.sub.j O.sub.x is used in the first-stage reaction, which is carried out under specific reaction and operational conditions, and the second-stage reaction is carried under specific reaction and operational conditions while oxygen is supplied by a specific mode.Type: GrantFiled: January 29, 1980Date of Patent: December 21, 1982Assignee: Mitsubishi Petrochemical Company LimitedInventors: Koju Kadowaki, Kohei Sarumaru, Takeshi Shibano
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Patent number: 4354044Abstract: A method for preparing methacrolein by oxidizing isobutylene or tertiary butanol with molecular oxygen, characterized by contacting a gaseous mixture of isobutylene or tertiary butanol, air or oxygen and optionally steam and an inert gas with a catalyst having the general combination:Mo.sub.12 Fe.sub.a Ni.sub.b Te.sub.c Tl.sub.d Pb.sub.f X.sub.g O.sub.hwherein a, b, c, d, f and g represent the numbers of atoms of the respective elements per 12 molybdenum atoms; X is at least one element selected from the group consisting of Cu, Nd and Sm; a is a value of 0.2-6; b is a value of 0.2-6; a+b is a value of 1-10; c is a value of 0.1-4; d is a value of 0.1-3; f is a value of 0.1-5; g is a value of 0.1-5; and h is the number of oxygen atoms for satisfying the valencies of the existing elements. The use of this catalyst enables the selectivity for methacrolein to be improved to 90-94% and the yield based on the starting material to be increased to 89-91%.Type: GrantFiled: May 20, 1981Date of Patent: October 12, 1982Assignee: Asahi Kasei Kogyo Kabushiki KaishaInventors: Atsushi Aoshima, Ryoichi Mitsui, Hitoshi Nihei
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Patent number: 4350830Abstract: A method for preparing acrylic acid by oxidation of acrolein over a new and improved catalyst providing conversions of acrolein of greater than 99% with yields of acrylic acid in excess of 95%. The catalyst consists essentially of the oxides of molybdenum, vanadium, chromium, copper and titanium and optionally silicon on an inert carrier. Catalysts useful in the process contain the elements previously mentioned in the atomic ratios ofMo.sub.15 V.sub.5-10 Cu.sub.2-5 Cr.sub.0.2-2 Ti.sub.Type: GrantFiled: October 17, 1979Date of Patent: September 21, 1982Assignee: The Dow Chemical Co.Inventors: David L. Childress, William V. Hayes, Richard L. Poppe
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Patent number: 4335264Abstract: The catalytic vapor phase oxidation of an olefin of 3 to 5 carbon atoms to .alpha.,.beta.-unsaturated aldehydes with the formation of substantially no .alpha.,.beta.-unsaturated acids is achieved by contacting the olefin, oxygen, an inert gas or moderator and optionally water with a catalyst at a temperature of from 300.degree. C. to 500.degree. C. for a period of time sufficient to achieve from 25 to 80% conversion of said olefin to said aldehyde, separating unreacted olefin and byproduct inert gas from the product stream and recycling the unreacted olefin and byproduct inert gas together with additional olefin and oxygen if required to react with said catalyst.Type: GrantFiled: July 7, 1976Date of Patent: June 15, 1982Assignee: E. I. Du Pont de Nemours and CompanyInventor: Paul C. Yates
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Patent number: 4335056Abstract: In the recovery of acrylonitrile from the gross reaction product produced during the commercial ammoxidation of propylene to produce acrylonitrile, an ammoxidation waste gas containing at least 65% nitrogen, carbon dioxide, carbon monoxide and a small amount of unreacted propylene is produced. In accordance with the invention, this ammoxidation waste gas is passed through a catalytic converter containing an oxidation or ammoxidation catalyst to convert the unreacted propylene into valuable product.Type: GrantFiled: January 5, 1981Date of Patent: June 15, 1982Assignee: Standard Oil CompanyInventors: James L. Callahan, Wilfrid G. Shaw, David B. Terrill
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Patent number: 4332971Abstract: Olefin oxidation catalysts having improved attrition resistance are produced by incorporating a substantially uniform-appearing coating of a partially calcined catalytic material onto an inert porous support containing sorbed aqueous silica sol and then completing the calcination of the catalyst. Such catalysts are useful in a variety of exothermic chemical processes, including vapor phase oxidation of olefinically unsaturated hydrocarbons to the corresponding unsaturated aldehydes, especially propylene to acrolein.Type: GrantFiled: December 15, 1980Date of Patent: June 1, 1982Assignee: Celanese CorporationInventors: Charles A. Dalton, William E. Slinkard
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Patent number: 4323520Abstract: The present invention relates to a process for the conversion of tertiary-butyl-containing compounds to methacrylic derivatives, and more particularly to a process for the conversion of tertiary-butyl-containing compounds selected from the group consisting of alkyl tertiary-butyl ethers, tertiary-butyl alcohol, isobutylene dimer (2,2,4-trimethylpentene) and isobutylene trimer, to methacrolein, methacrylic acid or methacrylonitrile.Type: GrantFiled: May 9, 1977Date of Patent: April 6, 1982Assignee: The Standard Oil Co.Inventors: Harley F. Hardman, James L. Callahan, Robert K. Grasselli
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Patent number: 4323703Abstract: The process comprises the vapor phase oxidation of lower molecular weight olefins to the corresponding unsaturated aldehydes and unsaturated carboxylic acids in the presence of a catalyst comprising the oxides of iron, bismuth, molybdenum and at least one element of the Group II elements as essential components, and optionally the oxides of phosphorus, arsenic and an alkali metal.Type: GrantFiled: May 26, 1977Date of Patent: April 6, 1982Assignee: Standard Oil CompanyInventors: Robert K. Grasselli, Arthur F. Miller, Harley F. Hardman
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Patent number: 4306090Abstract: Methacrolein is produced by the catalytic vapor phase oxidation of isobutylene (including compounds converted to isobutylene). The catalyst has the following formula: Mo.sub.a P.sub.b Fe.sub.c Co.sub.d Ni.sub.e Bi.sub.f Te.sub.g Sb.sub.h Cs.sub.i Zr.sub.j X.sub.k O.sub.x wherein a-k represent the number of atoms of the particular element depicted, X is another element and x is the number of oxygens present.Type: GrantFiled: August 29, 1980Date of Patent: December 15, 1981Assignee: Rohm and Haas CompanyInventors: Lawrence S. Kirch, William J. Kennelly
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Patent number: 4306088Abstract: In the production of methacrolein by vapor phase catalytic oxidation of isobutylene and/or t-butyl alcohol, an improved process for suppressing the amount of acetone to be by-produced which comprises contacting a gaseous mixture comprising isobutylene or t-butyl alcohol, molecular oxygen and steam with a metal oxide catalyst composition comprising molybdenum and bismuth as the essential metal components, the amount of steam in the gaseous mixture being kept to be not more than 4 mol per mol of isobutylene or not more than 3 mol per mol of t-butyl alcohol.Type: GrantFiled: June 25, 1980Date of Patent: December 15, 1981Assignee: Sumitomo Chemical Company, LimitedInventors: Shuzo Nakamura, Hiroshi Ichihashi, Yoshihiko Nagaoka, Koichi Nagai
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Patent number: 4298763Abstract: Acrolein and methacrolein are prepared advantageously by oxidizing propylene or isobutylene, respectively, with an oxygen-containing gas mixture under conventional conditions over a supported catalyst possessing a firmly adhering coating, from 150 to 1,500 .mu.m thick, which contains calcined catalytic material based on molybdenum oxide and has a carrier core with a surface area of less than 15 m.sup.2 /g and a diameter of more than 100 .mu.m, if a coated catalyst is used which has been prepared by applying calcined catalytic material having a particle size of from 0.1 to 300 .mu.m, in an amount of from 1 to 40 g/min/liter of carrier and water in a weight ratio of catalytic material to water of from 1:1 to 8:1, continuously and separately from one another, each at a constant speed, at below 100.degree. C.Type: GrantFiled: March 3, 1980Date of Patent: November 3, 1981Assignee: BASF AktiengesellschaftInventors: Heinz Engelbach, Richard Krabetz, Gerd Duembgen, Carl-Heinz Willersinn, Walter Beitelschmidt
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Patent number: 4267386Abstract: This invention provides an improved catalyst for vapor phase oxidation of propylene or isobutylene to the corresponding acrolein or methacrolein product. In a preferred embodiment, the oxidation catalyst corresponds to the formula:Mo.sub.12 Co.sub.4-5 Fe.sub.2-4 Ni.sub.2-3 Bi.sub.0.5-2 K.sub.0.65-1.3 P.sub.0.35-0.5 O.sub.xThis invention further provides a method of preparing the improved oxidation catalyst which in one important aspect of the preparation involves controlling the pH of an aqueous slurry admixture of catalyst components within the range of about 1-5.Type: GrantFiled: September 19, 1979Date of Patent: May 12, 1981Assignee: Celanese CorporationInventor: Thomas H. Vanderspurt
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Patent number: 4267385Abstract: Acrolein or methacrolein is produced in a high percent of yield by a catalytic oxidation of propylene or isobutylene in the presence of a catalyst of the empirical formula:Mo.sub.10 Co.sub.0.about.10 Ni.sub.0.about.10 Fe.sub.0.1.about.5 Bi.sub.0.001.about.3 Al.sub.0.05.about.10 Ti.sub.1.about.15 A.sub.0.about.4 O.sub.33.2.about.99wherein A denotes at least one alkali metal atom and the sum of the numbers of cobalt atoms and the nickel atoms is 1 to 10 per 10 atoms of molybdenum, which catalyst has an excellent crushing strength and exhibits a high catalyst activity.Type: GrantFiled: December 12, 1979Date of Patent: May 12, 1981Assignee: UBE Industries, Ltd.Inventors: Sumio Umemura, Kyoji Ohdan, Hiroyuki Asada
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Patent number: 4250339Abstract: Methacrolein is produced by a vapor phase oxidation of isobutylene or tertiary butanol in the presence of a complex oxide catalyst having the formulaMo.sub.a Co.sub.b Fe.sub.c Bi.sub.d Tl.sub.e X.sub.f Y.sub.g Z.sub.h O.sub.iwherein X represents V and/or Nb; Y represents La and/or Ce; and Z represents Cs and/or Te and a, b, c, d, e, f, g, h and i represent atomic ratios wherein a=12; b=3 to 15; c=0.4 to 5; d=0.4 to 5; e=0.01 to 2; f=0.01 to 2; g=0 to 2; h=0 to 2; and i is determined by the valences of the non-oxygen components of the catalyst and is usually in a range of 40 to 79.Type: GrantFiled: November 30, 1979Date of Patent: February 10, 1981Assignee: Toyo Soda Manufacturing Co., Ltd.Inventors: Teruhisa Sakamoto, Kazuhiko Sekizawa, Keiichi Kihara
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Patent number: 4226798Abstract: A method is disclosed for using a pendulum viscometer having damped torsional oscillations, in a laboratory catalytic fluid-bed reactor, to monitor a propensity to stick which is exhibited by certain supported catalysts. A fluid-bed of such catalysts has been found to become suddenly more sticky just before a point at which a change in pressure drop across the fluid-bed can be measured due to a process "upset". At this point ("the inversion point"), the upset is usually irremediable. The method includes correlating data on catalyst stickiness from a laboratory reactor operating at atmospheric pressure, with an expected level of catalyst stickiness in a commercial reactor operating at elevated pressure.A pendulum viscometer and related auxiliary apparatus is disclosed for magnetically and electrically measuring and recording the rate at which the pendulum's torsional oscillations are damped.Type: GrantFiled: October 6, 1978Date of Patent: October 7, 1980Assignee: The B. F. Goodrich CompanyInventors: Joseph A. Cowfer, Dane E. Jablonski, Ronald M. Kovach, Angelo J. Magistro
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Patent number: 4217309Abstract: Methacrolein is produced in a high yield by catalytically oxidizing isobutylene at a temperature of from 250.degree. to 500.degree. C. by using a catalyst represented by the formula:Mo.sub.a Co.sub.b Fe.sub.c Bi.sub.d Cs.sub.e X.sub.f Y.sub.g O.sub.hwherein X is either both vanadium and palladium, Y is at least one member selected from titanium, nickel, tin and zirconium, a=12, b=2-12, c=0.5-7, d=0.1-5, e=0.0005-0.5, f=0.01-2, g=0-5 and h is a positive number proportional to the number of oxygen atoms satisfying the average valency of the metal atoms stated in the formula, which catalyst has a high resistance to compression and abrasion and exhibits a high catalytic efficiency, mechanical strength and durability.Type: GrantFiled: February 28, 1979Date of Patent: August 12, 1980Assignee: Ube Industries, Ltd.Inventors: Sumio Umemura, Kyoji Ohdan, Kenichi Suzuki, Yasuo Bando, Terumi Hisayuki
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Patent number: 4203906Abstract: A process for catalytic vapor phase oxidation which comprises using a fixed-bed shell and tube heat exchange type reactor in which a bundle of a multiplicity of tubes filled with at least one type of oxidizing catalyst are disposed in a shell and these tubes are passed through the apertures formed in at least one perforated shield plate to partition the inside of the shell into at least two heat transfer medium feed zones and in such a manner that each of the tubes passing through the perforated shield plate is not in direct contaction with the shield plate but the outer surface of the tube and the inner surface of the aperture are spaced apart by a distance of between 0.2-5 mm, supplying feed gas to the tubes of the reactor, and conducting exothermic catalytic vapor phase oxidation while controlling the temperatures for the heat transfer medium in each of the zones so that the temperature difference between each of the zones can be maintained between 0.degree.-100.degree. C.Type: GrantFiled: July 7, 1978Date of Patent: May 20, 1980Assignee: Nippon Shokubai Kagaku Kogyo Co., Ltd.Inventors: Masahiro Takada, Hiroyuki Uhara, Takahisa Sato